Planarization layer for organic electronic devices

ABSTRACT

The invention relates to organic electronic devices containing polycycloolefin planarization layers between the substrate and a functional layer like a semiconducting layer, dielectric layer or electrode, to the use of polycycloolefins as planarization layer on the substrate of an organic electronic device, and to processes for preparing such polycycloolefin planarization layers and organic electronic devices.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims benefit to U.S. Provisional Application No.61/599,069 filed Feb. 15, 2012 and EP Application No. 12000974.1 filedon Feb. 15, 2012 which both are incorporated by reference in itsentirety.

TECHNICAL FIELD

Embodiments in accordance with the present invention relate to organicelectronic devices comprising polycycloolefin planarization layers, andmore particularly to planarization layers positioned between thesubstrate and a functional layer, e.g. a semiconducting layer, adielectric layer or an electrode, and further to the use of such aplanarization layer in organic electronic devices, and to processes forpreparing such polycycloolefin planarization layers and organicelectronic devices.

BACKGROUND

In recent years there has been growing interest in organic electronic(OE) devices, for example field effect transistors for use in displaydevices and logic capable circuits, or organic photovoltaic (OPV)devices. A conventional organic field effect transistor (OFET) typicallyincludes source, drain and gate electrodes, a semiconducting layer madeof an organic semiconductor (OSC) material, and an insulator layer (alsoreferred to as “dielectric” or “gate dielectric”), made of a dielectricmaterial and positioned between the OSC layer and the gate electrode.

A broad range of different substrates can be used for OE devices likeOFETs and OPVs. The most common are polymers like polyethyleneterephthalate (PET), polyethylene naphthalate (PEN), other polyesters,polyimide, polyacrylate, polycarbonate, polyvinylalcohol,polycycloolefin or polyethersulphone. Thin metal films, paper basedsubstrates, glass and others are also available.

However, the substrates that have hitherto been available often containdefects and contamination from the production process. Therefore, forthe purpose of integrity of the thin-film OE devices made on top ofthem, most of these substrates require an additional planarization orbarrier layer in order to provide a smooth and defect-free surface.

Further reasons or functions requiring the application of anintermediate layer between substrate and OSC material include: 1)improving the hardness/scratch resistance of the substrate, 2) providingelectrical isolation of the substrate and the OSC layer, 3) providing abarrier to prevent diffusion of metal ions, small molecules, andoligomers from the carrier substrate to OSC, 4) modifying wettingproperties of the substrate, and 5) acting as adhesion promoter.

Various plastic film substrates are commercially available, like forexample PET films of the Melinex® series or PEN films of the Teonex®series, both from DuPont Teijin Films™

Typical commercially available planarization, hard-coating, or barriermaterials include:

1) Silicon dioxide (SiO₂) or silicon nitride (SiNX) electricalinsulators, which are used mainly on top of conducting metal substrates.

2) Organic polymers, such as, acrylic-, melamine- or urethane-basedpolymers.

3) Organic-inorganic hybrid composites, which are based mainly on theuse of metal alkoxide and organosiloxane via sol-gel processing, asdisclosed for example in U.S. Pat. No. 5,976,703 or in W. Tanglumlert etal. ‘Hard-coating materials for poly(methyl methacrylate) fromglycidoxypropyl-trimethoxysilane-modified silatrane via sol-gelprocess’, Surface & Coatings Technology 200 (2006) p. 2784.

Nevertheless, to date there has been no planarization material whichfulfils all requirements for all the commercially available OE/OPVmaterials. Two of the major weaknesses of the currently availablematerials are: 1) a low surface energy, which causes de-wetting of OSCmaterials during coating, therefore requiring additional pre-treatment,and 2) a high permeation of the available polymers and composites towater. Therefore, the above-mentioned materials are not suitable formany OE/OPV applications unless an additional barrier or surfacemodification layer is applied.

Moreover, the inventors have found that the planarization materials usedin commercially available PET or PEN substrates have turned out not tobe fully compatible with recently developed high performance OSCmaterials, like those of the Lisicon® Series (commercially availablefrom Merck KGaA or Merck Chemicals Ltd.). Further, poor electricalstability of devices using the Lisicon® Series OSC directly on top ofplanarised Melinex® and Teonex® has been observed. Therefore, anadditional barrier/surface modification layer on top of the existingplanarization layer, or a replacement for the planarization layer wouldbe advantageous.

In general, a planarization material should exhibit one or more of thefollowing characteristics:

1). acting as an electrical insulator,

2). providing a smooth surface (preferably arithmetic average roughnessof absolute values (Ra)<5 and maximum high of the profile (Rt)<50),

3). providing for the electrical performance and stability of OTFTscompared to the best working example on any other substrate,

4). enabling good adhesion between the substrate and electrode metals(preferably 5N/cm or higher),

5). possessing good wetting properties for OSC formulations (preferablya surface energy of the planarization layer≧50 mN/m),

6). inherent resistance to process chemicals,

7). optical transparency in the visible spectrum,

8). deposition using well established industrial processes.

Therefore, there is still a need for improved planarization layers whichcan be used in OE devices, especially OFETs and OPV cells, which fulfilthe above-mentioned requirements.

One aim of the present invention is to provide planarization layersmeeting these requirements. Another aim is to provide improved OE/OPVdevices comprising such planarization layers. Further aims areimmediately evident to the person skilled in the art from the followingdescription.

The inventors of the present invention have found these aims can beachieved by providing planarization layers and OE devices in accordancewith the present invention and as claimed hereinafter.

SUMMARY OF THE INVENTION

Embodiments in accordance with the present invention encompass anorganic electronic device overlying a substrate, the substrate having aplanarization layer provided between the substrate and a functionallayer, where the planarization layer encompasses a polycycloolefinicpolymer and the functional layer is one of a semiconducting layer, adielectric layer or an electrode.

Some embodiments in accordance with the present invention are alsodirected to the use of the aforementioned planarization layer in anorganic electronic device. Still further, some embodiments are directedto a method of using a polycycloolefinic polymer in the fabrication of aplanarization layer for an organic electronic device.

The aforementioned polycycloolefinic polymer is for example anorbornene-type polymer.

The aforementioned organic electronic device is for example an OrganicField Effect Transistor (OFET), which is inclusive of an Organic ThinFilm Transistor (OTFT), a top gate OFET, a bottom gate OFET, an OrganicPhotovoltaic (OPV) Device or an Organic Sensor.

Embodiments of the present invention are also inclusive of a product oran assembly encompassing an organic electronic device as described aboveand below. Such product or assembly being an Integrated Circuit (IC), aRadio Frequency Identification (RFID) tag, a security marking orsecurity device containing an RFID tag, a Flat Panel Display (FPD), abackplane of an FPD, or a sensor.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments in accordance with the present invention are described belowwith reference to the following drawings.

FIG. 1 is a schematic representation of a top gate OFET device accordingto prior art;

FIG. 2 is a schematic representation of a bottom gate OFET deviceaccording to prior art;

FIG. 3 is a schematic representation of a top gate OFET device inaccordance with an embodiment of the present invention;

FIG. 4 is a schematic representation of a bottom gate OFET device inaccordance with an embodiment of the present invention;

FIG. 5 is a transfer curve of the top gate OFET device of ComparisonExample 1;

FIG. 6 is a transfer curve of the top gate OFET device of Example 1;

FIG. 7 is a transfer curve of the top gate OFET device of ComparisonExample 2;

FIG. 8 is a transfer curve of the top gate OFET device of Example 2; and

FIG. 9 is a transfer curve of the top gate OFET device of Example 3.

DETAILED DESCRIPTION OF THE INVENTION

Exemplary embodiments in accordance with the present invention will bedescribed with reference to the Examples and Claims providedhereinafter. Various modifications, adaptations or variations of suchexemplary embodiments described herein may become apparent to thoseskilled in the art as such are disclosed. It will be understood that allsuch modifications, adaptations or variations that rely upon theteachings of the present invention, and through which these teachingshave advanced the art, are considered to be within the scope of thepresent invention.

As used herein, the articles “a,” “an,” and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Since all numbers, values and/or expressions referring to quantities ofingredients, reaction conditions, etc., used herein and in the Exhibitsand Claims appended hereto, are subject to the various uncertainties ofmeasurement encountered in obtaining such values, unless otherwiseindicated, all are to be understood as modified in all instances by theterm “about.”

Where a numerical range is disclosed herein, unless otherwise specified,such range is continuous, inclusive of both the minimum and maximumvalues of the range as well as every value between such minimum andmaximum values. Still further, where a range refers to integers, everyinteger between the minimum and maximum values of such range isincluded. In addition, where multiple ranges are provided to describe afeature or characteristic, such ranges can be combined. That is to saythat, unless otherwise indicated, all ranges disclosed herein are to beunderstood to encompass any and all subranges subsumed therein. Forexample, a stated range of from “1 to 10” should be considered toinclude any and all subranges between the minimum value of 1 and themaximum value of 10. Exemplary subranges of the range 1 to 10 include,but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

Advantageously, the polycycloolefinic or norbornene-type polymers usedin the planarization layers of the present invention are tailorable toovercome the drawbacks that have been observed in previously knownplanarization materials, such as poor electrical stability of the OSC incontact with the planarization layer, low surface energy which causesde-wetting of the OSC material during coating.

Moreover, the planarization layers comprising polycycloolefinic polymersshow improved adhesion to the substrate and to electrodes, reducedsurface roughness, and improved OSC performance.

The planarization layers comprising polycycloolefinic polymers allow fortime-, cost- and material-effective production of OFETs employingorganic semiconductor materials and organic dielectric materials on alarge scale.

Further, as will be discussed, the polycycloolefinic or norbornene-typepolymers can, in combination with the substrate and/or with functionallayers like the organic dielectric layer or the OSC layer, provideimproved surface energy, adhesion and structural integrity of suchcombined layers in comparison with planarization materials of prior artthat have been employed in such OFETs.

As used herein, the term “polymer” will be understood to mean a moleculethat encompasses a backbone of one or more distinct types of repeatingunits (the smallest constitutional unit of the molecule) and isinclusive of the commonly known terms “oligomer”, “copolymer”,“homopolymer” and the like. Further, it will be understood that the termpolymer is inclusive of, in addition to the polymer itself, residuesfrom initiators, catalysts and other elements attendant to the synthesisof such a polymer, where such residues are understood as not beingcovalently incorporated thereto. Further, such residues and otherelements, while normally removed during post polymerization purificationprocesses, are typically mixed or co-mingled with the polymer such thatthey generally remain with the polymer when it is transferred betweenvessels or between solvents or dispersion media.

As used herein, the terms “orthogonal” and “orthogonality” will beunderstood to mean chemical orthogonality. For example, an orthogonalsolvent means a solvent which, when used in the deposition of a layer ofa material dissolved therein on a previously deposited layer, does notdissolve said previously deposited layer.

As used herein, the term “polymer composition” means at least onepolymer and one or more other materials added to the at least onepolymer to provide, or to modify, specific properties of the polymercomposition and or the at least one polymer therein. It will beunderstood that a polymer composition is a vehicle for carrying thepolymer to a substrate to enable the forming of layers or structuresthereon. Exemplary materials include, but are not limited to, solvents,antioxidants, photoinitiators, photosensitizers, crosslinking moietiesor agents, reactive diluents, acid scavengers, leveling agents andadhesion promoters. Further, it will be understood that a polymercomposition may, in addition to the aforementioned exemplary materials,also encompass a blend of two or more polymers.

As defined herein, the terms “polycycloolefin”, “polycyclic olefin”, and“norbornene-type” are used interchangeably and refer to additionpolymerizable monomers, or the resulting repeating unit, encompassing atleast one norbornene moiety such as shown by either Structure A1 or A2,below. The simplest norbornene-type or polycyclic olefin monomerbicyclo[2.2.1]hept-2-ene (A1) is commonly referred to as norbornene.

However, the term “norbornene-type monomer” or “norbornene-typerepeating unit”, as used herein, is understood to not only meannorbornene itself but also to refer to any substituted norbornene, orsubstituted and unsubstituted higher cyclic derivatives thereof, forexample of Structures B1 and B2, shown below, wherein m is an integergreater than zero.

By the substitution of a norbornene-type monomer with a pendant group,the properties of a polymer formed therefrom can be tailored to fulfillthe needs of individual applications. The procedures and methods thathave been developed to polymerize functionalized norbornene-typemonomers exhibit an outstanding flexibility and tolerance to variousmoieties and groups of the monomers. In addition to polymerization ofmonomers with a specific pendant group, monomers having a variety ofdistinct functionalities can be randomly polymerized to form a finalmaterial where the types and ratios of monomers used dictate the overallbulk properties of the resulting polymer.

As used herein, “hydrocarbyl” refers to a radical or group that containsa carbon backbone where each carbon is appropriately substituted withone or more hydrogen atoms. The term “halohydrocarbyl” refers to ahydrocarbyl group where one or more of the hydrogen atoms, but not all,have been replaced by a halogen (F, Cl, Br, or I). The termperhalocarbyl refers to a hydrocarbyl group where each hydrogen has beenreplaced by a halogen. Non-limiting examples of hydrocarbyls, include,but are not limited to a C₁-C₂₅ alkyl, a C₂-C₂₄ alkenyl, a C₂-C₂₄alkynyl, a C₅-C₂₅ cycloalkyl, a C₆-C₂₄ aryl or a C₇-C₂₄ aralkyl.Representative alkyl groups include but are not limited to methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl.Representative alkenyl groups include but are not limited to vinyl,propenyl, butenyl and hexenyl. Representative alkynyl groups include butare not limited to ethynyl, 1-propynyl, 2-propynyl, 1 butynyl, and2-butynyl. Representative cycloalkyl groups include but are not limitedto cyclopentyl, cyclohexyl, and cyclooctyl substituents. Representativearyl groups include but are not limited to phenyl, biphenyl, naphthyl,and anthracenyl. Representative aralkyl groups include but are notlimited to benzyl, phenethyl and phenbutyl.

The term “halohydrocarbyl” as used herein is inclusive of thehydrocarbyl moieties mentioned above but where there is a degree ofhalogenation that can range from at least one hydrogen atom beingreplaced by a halogen atom (e.g., a fluoromethyl group) to where allhydrogen atoms on the hydrocarbyl group have been replaced by a halogenatom (e.g., trifluoromethyl or perfluoromethyl), also referred to asperhalogenation. The term “perhalohydrocarbyl”=as used herein isinclusive of the hydrocarbyl moieties mentioned above but where all thehydrogen atom being replaced by a halogen atom. For example, halogenatedalkyl groups that can be useful in embodiments of the present inventioncan be partially or fully halogenated, alkyl groups of the formulaC_(a)X_(2a+1) wherein X is independently a halogen or a hydrogen and ais selected from an integer of 1 to 25. In some embodiments each X isindependently selected from hydrogen, chlorine, fluorine bromine and/oriodine. In other embodiments each X is independently either hydrogen orfluorine. Thus, representative halohydrocarbyls and perhalocarbyls areexemplified by the aforementioned exemplary hydrocarbyls where anappropriate number of hydrogen atoms are each replaced with a halogenatom.

In addition, the definition of the terms “hydrocarbyl”,“halohydrocarbyl”, and “perhalohydrocarbyl”, are inclusive of moietieswhere one or more of the carbons atoms is replaced by a heteroatomselected independently from O, N, P, or Si. Such heteroatom containingmoieties can be referred to as, for example, either“heteroatom-hydrocarbyls” or “heterohydrocarbyls”, including, amongothers, ethers, epoxies, glycidyl ethers, alcohols, carboxylic acids,esters, maleimides, amines, imines, amides, phenols, amido-phenols,silanes, siloxanes, phosphines, phosphine oxides, phosphinites,phosphonites, phosphites, phosphonates, phosphinates, and phosphates.

Further exemplary hydrocarbyls, halohydrocarbyls, and perhalocarbyls,inclusive of heteroatoms, include, but are not limited to,—(CH₂)_(n)—Ar—(CH₂)_(n)—C(CF₃)₂—OH,—(CH₂)_(n)—Ar—(CH₂)_(n)—OCH₂C(CF₃)₂—OH, —(CH₂)_(n)—C(CF₃)₂—OH,—((CH₂)₁—O—)_(k)—(CH₂)—C(CF₃)₂—OH, —(CH₂)_(n)—C(CF₃)(CH₃)—OH,—(CH₂)_(n)—C(O)NHR*, —(CH₂)_(n)—C(O)Cl, —(CH₂)_(n)—C(O)OR*,—(CH₂)_(n)—OR*, —(CH₂)_(n)—OC(O)R* and —(CH₂)_(n)—C(O)R*, where nindependently represents an integer from 0 to 12, i is 2, 3 or 4, k is1, 2 or 3, Ar is aryl, for example phenyl, and R* independentlyrepresents hydrogen, a C₁-C₁₁ alkyl, a C₁-C₁₁ halogenated orperhalogenated alkyl, a C₂-C₁₀ alkenyl, a C₂-C₁₀ alkynyl, a C₅-C₁₂cycloalkyl, a C₆-C₁₄ aryl, a C₆-C₁₄ halogenated or perhalogenated aryl,a C₇-C₁₄ aralkyl or a halogenated or perhalogenated C₇-C₁₄ aralkyl.

Exemplary perhalogenated alkyl groups include, but are not limited to,trifluoromethyl, trichloromethyl, —C₂F₅, —C₃F₇, —C₄F₉, —C₆F₁₃, —C₇F₁₅,and —C₁₁F₂₃. Exemplary halogenated or perhalogenated aryl and aralkylgroups include, but are not limited to, groups having the formula—(CH₂)_(x)—C₆F_(y)H_(5−y), and—(CH₂)_(x)—C₆F_(y)H_(4−y−p)C_(z)F_(q)H_(2z+1−q), where x, y, q and z areindependently selected integers from 0 to 5, 0 to 5, 0 to 9 and 1 to 4,respectively. Specifically, such exemplary halogenated or perhalogenatedaryl groups include, but are not limited to, pentachlorophenyl,pentafluorophenyl, pentafluorobenzyl, 4-trifluoromethylbenzyl,pentafluorophenethyl, pentafluorophenpropyl, and pentafluorophenbutyl.

In some polymer embodiments in accordance with the invention, thenorbornene-type polymer incorporates two or more distinct types ofrepeating units.

In other polymer embodiments in accordance with the invention, thenorbornene-type polymer incorporates one or more distinct types ofrepeating units, where at least one such type of repeating unitencompasses pendant crosslinkable groups or moieties that have somedegree of latency. By “latency”, it is meant that such groups do notcrosslink at ambient conditions or during the initial forming of thepolymers, but rather crosslink when such reactions are specificallyinitiated, for example by actinic radiation or heat. Such latentcrosslinkable groups are incorporated into the polymer backbone by, forexample, providing one or more norbornene-type monomers encompassingsuch a pendant crosslinkable group, for example, a substituted orunsubstituted maleimide or maleimide containing pendant group, to thepolymerization reaction mixture and causing the polymerization thereof.Other examples of crosslinkable groups encompass a group comprising asubstituted or unsubstituted maleimide portion, an epoxide portion, avinyl portion, an acetylene portion, an indenyl portion, a cinnamateportion or a coumarin portion, and more specifically a group selectedfrom a 3-monoalkyl- or 3,4-dialkylmaleimide, epoxy, vinyl, acetylene,cinnamate, indenyl or coumarin group.

Other polymer embodiments in accordance with the invention contain oneor more norbornene-type polymers having one or more distinct types ofrepeating units of formula I

wherein Z is selected from —CH₂—, —CH₂—CH₂— or —O—, m is an integer from0 to 5, each of R¹, R², R³ and R⁴ are independently selected from H, aC₁ to C₂₅ hydrocarbyl, a C₁ to C₂₅ halohydrocarbyl or a C₁ to C₂₅perhalocarbyl group.

The repeating units of Formula I are formed from the correspondingnorbornene-type monomers of Formula Ia where Z, m and R¹-R⁴ are asdefined above:

For some polymer embodiments in accordance with the present invention,for the repeating units and monomers of Formula I and Ia, Z is —CH₂— andm is 0, 1 or 2. For other such polymer embodiments Z is —CH₂— and m is 0or 1, and for still other embodiments, Z is —CH₂— and m is 0.

Some embodiments of the invention encompass an organic electronic deviceoverlying a substrate, the substrate having a planarization layerprovided between the substrate and a functional layer, where theplanarization layer encompasses a polymer composition that comprises apolycycloolefinic polymer, and the functional layer is one of asemiconducting layer, a dielectric layer or an electrode.

Polymer composition embodiments in accordance with the inventionencompass either a single norbornene-type polymer or a blend of two ormore different norbornene-type polymers. Where such polymer compositionembodiments encompass a single norbornene-type polymer, such polymer canbe a homopolymer, that is to say a polymer encompassing only one type ofrepeating unit, or a copolymer, that is to say a polymer encompassingtwo or more distinct types of repeating units. Where such polymercomposition embodiments encompass a blend of different polymers,“different” is understood to mean that each of the blended polymersencompasses at least one type of repeating unit, or combination ofrepeating units, that is distinct from any of the other blendedpolymers.

Other polymer composition embodiments of the invention encompass a blendof two or more different norbornene-type polymers, wherein each polymercomprises one or more distinct types of repeating units of formula I

wherein Z is selected from —CH₂—, —CH₂—CH₂— or —O—, m is an integer from0 to 5, each of R¹, R², R³ and R⁴ are independently selected from H, aC₁ to C₂₅ hydrocarbyl, a C₁ to C₂₅ halohydrocarbyl or a C₁ to C₂₅perhalocarbyl group.

The polymer and polymer composition embodiments of the present inventioncan advantageously be tailored to provide a distinct set of propertiesfor each of many specific applications. That is to say that differentcombinations of norbornene-type monomers with several different types ofpendant groups can be polymerized to provide norbornene-type polymershaving properties that provide for obtaining control over propertiessuch as flexibility, adhesion, dielectric constant, and solubility inorganic solvents, among others. For example, varying the length of analkyl pendant group can allow control of the polymer's modulus and glasstransition temperature (Tg). Also, pendant groups selected frommaleimide, cinnamate, coumarin, anhydride, alcohol, ester, and epoxyfunctional groups can be used to promote crosslinking and to modifysolubility characteristics. Polar functional groups, epoxy andtriethoxysilyl groups can be used to provide adhesion to metals,silicon, and oxides in adjacent device layers. Fluorinated groups, forexample, can be used to effectively modify surface energy, dielectricconstant and influence the orthogonality of the solution with respect toother materials.

Thus, in further embodiments of the present invention, in particular forsuch embodiments where only one of R¹⁻⁴ is different from H, one or moreof R¹⁻⁴ denote a halogenated or perhalogenated aryl or aralkyl groupincluding, but not limited to those of the formula—(CH₂)_(x)—C₆F_(y)H_(5−y), and—(CH₂)_(x)—C₆F_(y)H_(4−y−p)C_(z)F_(q)H_(2z+1−q), where x, y, q, and zare independently selected integers from 0 to 5, 0 to 5, 0 to 9, and 1to 4, respectively, and “p” means “para”. Specifically such formulaeinclude, but are not limited to, trifluoromethyl, trichloromethyl,—C₂F₅, —C₃F₇, —C₄F₉, C₆F₁₃, —C₇F₁₅, —C₁₁F₂₃, pentachlorophenyl,pentafluorophenyl, pentafluorobenzyl, 4-trifluoromethylbenzyl,pentafluorophenylethyl, pentafluorophenpropyl, and pentafluorophenbutyl.

Further still, some embodiments of the present invention, in particularfor such embodiments where only one of R¹⁻⁴ is different from H,encompass a group that is different from H that is a polar group havinga terminal hydroxy, carboxy or oligoethyleneoxy moiety, for example aterminal hydroxyalkyl, alkylcarbonyloxy (for example, acetyl),hydroxy-oligoethyleneoxy, alkyloxy-oligoethyleneoxy oralkylcarbonyloxy-oligoethyleneoxy moiety, where “oligoethyleneoxy” isunderstood to mean —(CH₂CH₂O)_(s)— with s being 1, 2 or 3; for example1-(bicyclo[2.2.1]hept-5-en-2-yl)-2,5,8,11-tetraoxadodecane (NBTODD)where s is 3 and5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene (NBTON)where s is 2.

Further still, other embodiments of the present invention, in particularfor such embodiments where only one of R¹⁻⁴ is different from H,encompass a group that is different from H that is a group having apendant silyl group, for example a silyl group represented by—(CH₂)_(n)—SiR⁹ ₃ where n is an integer from 0 to 12, and each R⁹independently represents halogen selected from the group consisting ofchlorine, fluorine, bromine and iodine, linear or branched (C₁ toC₂₀)alkyl, linear or branched (C₁ to C₂₀)alkoxy, substituted orunsubstituted (C₆ to C₂₀)aryl, linear or branched (C₁ to C₂₀)alkylcarbonyloxy, substituted or unsubstituted (C₆ to C₂₀)aryloxy; linear orbranched (C₁ to C₂₀) dialkylamido; substituted or unsubstituted (C₆-C₂₀)diarylamido; substituted or unsubstituted (C₁-C₂₀)alkylarylamido.

Yet further still, for such embodiments where only one of R¹⁻⁴ isdifferent from H, some embodiments encompass a group that is either aphotoreactive or a crosslinkable group. Photoreactive or crosslinkablegroups encompass a linking portion L and a functional portion Fp. Ldenotes or comprises a group selected from C₁-C₁₂ alkyls, aralkyls,aryls or hetero atom analogs. Further Fp denotes or comprises one ormore of a maleimide, a 3-monoalkyl- or 3,4-dialkylmaleimide, epoxy,vinyl, acetyl, cinnamate, indenyl or coumarin moiety, which is capableof a crosslinking or 2+2 crosslinking reaction.

As used herein, the phrase “photoreactive and/or crosslinkable”, whenused to describe certain pendant groups, will be understood to mean agroup that is reactive to actinic radiation and as a result of thatreactivity enters into a crosslinking reaction, or a group that is notreactive to actinic radiation but can, in the presence of a crosslinkingactivator, enter into a crosslinking reaction.

Exemplary repeating units that encompass a pendant photoreactive orcrosslinkable group that are representative of Formula I are formedduring polymerization from norbornene-type monomers that include, butare not limited to, those selected from the following formulae:

where n is an integer from 1 to 8, Q¹ and Q² are each independently fromone another —H or —CH₃, and R′ is —H or —OCH₃.

Further exemplary repeating units of Formula I such as described aboveare derived from one or more norbornene-type monomers represented by thefollowing structural formulae 1 through 5 below:

For structural formulae I-5 above, m is an integer from 0 to 3, A is aconnecting, spacer or bridging group selected from (CZ₂)_(n),(CH₂)_(n)—(CH═CH)_(p)—(CH₂)_(n), (CH₂)_(n)—O—(CH₂)_(n),(CH₂)_(n)—C₆Q₄-(CH₂)_(n), and for structure 1 additionally selected from(CH₂)_(n)—O and C(O)—O; R is selected from H, CZ₃, (CZ₂)_(n)CZ₃, OH,O—(O)CCH₃, (CH₂CH₂O)_(n)CH₃, (CH₂)_(n)—C₆Q₅, cinnamate orp-methoxy-cinnamate, coumarin, phenyl-3-indene, epoxide, C≡C—Si(C₂H₅)₃or C≡C—Si(i-C₂H₅)₃, each n is independently an integer from 0 to 12, pis an integer from 1-6, C₆Q₄ and C₆Q₅ denote benzene that is substitutedwith Q, Q is independently H, F, CH₃, CF₃ or OCH₃, Z is independently Hor F, with the proviso that -A-R does not contain an —O—O— (peroxy)linkage, and R″ is independently H or CH₃.

Further exemplary repeating units represented by Formula I, as describedabove, are formed from one or more norbornene-type monomers thatinclude, but are not limited to, those selected from the followingformulae:

where “Me” means methyl, “Et” means ethyl, “OMe-p” means para-methoxy,“Ph” and “C₆H₅” mean phenyl, “C₆H₄” means phenylene, “C₆F₅” meanspentafluorophenyl, in subformulae 9 and 11 “OAc” means acetate, insub-formula 25 “PFAc” means —OC(O)—C₇F₁₅, and for each of the abovesubformulae having a methylene bridging group (a CH₂ covalently bondedto both the norbornene ring and a functional group), including but notlimited to 11-14, 16, 18, 19 and 54, it will be understood that themethylene bridging group can be replaced by a covalent bond or—(CH₂)_(b)— as in formula 20, and b is an integer from 1 to 6.

It will be further noted that while 55 specific examples are providedabove, other monomers in accordance with embodiments of the presentinvention are inclusive of monomers represented by formula Ia where atleast one of R¹, R², R³ and R⁴ are hydrocarbyls, halohydrocarbyls, andperhalocarbyls, inclusive of heteroatoms, that include,—(CH₂)_(n)—Ar—(CH₂)_(n)—C(CF₃)₂—OH,—(CH₂)_(n)—Ar—(CH₂)_(n)—OCH₂C(CF₃)₂—OH, —(CH₂)_(n)—C(CF₃)₂—OH,—((CH₂)_(i)—O—)_(b)—(CH₂)—C(CF₃)₂—OH, —(CH₂)_(n)—C(CF₃)(CH₃)—OH,(CH₂)_(n)—C(O)NHR*, (CH₂)_(n)—C(O)Cl, —(CH₂)_(n)—C(O)OR*, (CH₂)_(n)—OR*,—(CH₂)_(n)—OC(O)R* and —(CH₂)_(n)—C(O)R*, where n independentlyrepresents an integer from 0 to 12, i is 2, 3 or 4, k is 1, 2 or 3, Aris aryl, for example phenyl, and R* independently represents hydrogen, aC₁-C₁₁ alkyl, a C₁-C₁₁ halogenated or perhalogenated alkyl, a C₂-C₁₀alkenyl, a C₂-C₁₀ alkynyl, a C₅-C₁₂ cycloalkyl, a C₆-C₁₄ aryl, a C₆-C₁₄halogenated or perhalogenated aryl, a C₇-C₁₄ aralkyl or a halogenated orperhalogenated C₇-C₁₄ aralkyl. Exemplary perhalogenated alkyl groupsinclude, but are not limited to, trifluoromethyl, trichloromethyl,—C₂F₅, —C₃F₇, —C₄F₉, —C₇F₁₅, and —C₁₁F₂₃. Exemplary halogenated orperhalogenated aryl and aralkyl groups include, but are not limitedgroups having the formula —(CH₂)_(x)—C₆F_(y)H_(5−y), and—(CH₂)_(x)—C₆F_(y)H_(4−y)-pC_(z)F_(q)H_(2z+1−q), where x, y, q, and zare independently selected integers from 0 to 5, 0 to 5, 0 to 9, and 1to 4, respectively. Specifically, such exemplary halogenated andperhalogenated aryl groups include, but are not limited to,pentachlorophenyl, pentafluorophenyl, pentafluorobenzyl,4-trifluoromethylbenzyl, pentafluorophenylethyl, pentafluorophenpropyl,and pentafluorophenbutyl.

While each Formula I and Ia, as well as each of the subformulae andgeneric formulae provided above are depicted without indication of anystereochemistry, it should be noted that generally each of the monomers,unless indicated otherwise, are obtained as diastereomeric mixtures thatretain their configuration when converted into repeating units. As theexo- and endo-isomers of such diastereomeric mixtures can have slightlydifferent properties, it should be further understood that embodimentsof the present invention are made to take advantage of such differencesby using monomers that are either a mixture of isomers that is rich ineither the exo- or endo-isomer, or are essentially the pure advantageousisomer.

Another embodiment of the present invention is directed to polymers ofFormula I that comprise repeating units where one of R¹⁻⁴, for exampleR¹, is a fluorinated or perfluorinated alkyl, aryl or aralkyl group asdescribed above and the others of R¹⁻⁴ are H. Another embodiment of thisinvention, R¹ is selected from one of the above subformulae 15-26 and inone embodiment from subformulae 15, 16, 17, 18, 19 or 20 (NBC₄F₉,NBCH₂C₆F₅, NBC₆F₅, NBCH₂C₆H₃F₂, NBCH₂C₆H₄CF₃, and NBalkylC₆F₅).

Another embodiment of the present invention is directed to polymers ofFormula I that have repeating units where one of R¹⁻⁴, for example R¹,is a photoreactive or crosslinkable group as described above and theothers of R¹⁻⁴ are H. R¹ is a group as shown in one of the abovesubformulae 27-50 and as shown in subformulae 34, 35, 36, 37 and 38(DMMIMeNB, DMMIEtNB, DMMIPrNB, DMMIBuNB and DMMIHxNB).

Another embodiment of the present invention is directed to polymers ofFormula I that have repeating units where one of R¹⁻⁴, for example R¹,is a pendant silyl group represented by —(CH₂)_(n)—SiR⁹³ where n is aninteger from 0 to 12, R⁹ independently represents halogen selected fromthe group consisting of chlorine, fluorine, bromine and iodine, linearor branched (C₁ to C₂₀)alkyl, linear or branched (C₁ to C₂₀)alkoxy,substituted or unsubstituted (C₆ to C₂₀)aryl, linear or branched (C₁ toC₂₀)alkyl carbonyloxy, substituted or unsubstituted (C₆ to C₂₀)aryloxy;linear or branched (C₁ to C₂₀) dialkylamido; substituted orunsubstituted (C₆-C₂₀) diarylamido; substituted or unsubstituted(C₁-C₂₀)alkylarylamido.

Another embodiment of the present invention is directed to polymers ofFormula I that have repeating units where one of R¹⁻⁴, for example R¹,is a polar group having a hydroxy, carboxy, acetoxy or oligoethyleneoxymoiety as described above and the others of R¹⁻⁴ denote H. Preferably R¹is a group as shown in one of the above subformulae 9-14, and generallyof subformula 9 (MeOAcNB).

Another embodiment of the present invention is directed to a polymerhaving a first type of repeating unit selected from fluorinatedrepeating units as described above and a second type of repeating unitselected from crosslinkable repeating units, also as described above.Polymers of this embodiment include polymers having a first type ofrepeating unit selected from subformulae 15, 16, 17, 18, 19 and 20(NBC₄F₉, NBCH₂C₆F₅, NBC₆F₅, NBCH₂C₆F₂, NBCH₂C₆H₄CF₃, NBalkylC₆F₅), and asecond type of repeating unit selected from subformulae 34, 35, 36, 37and 38 (DMMIMeNB, DMMIEtNB, DMMIPrNB, DMMIBuNB, DMMIHxNB).

Another embodiment of the present invention is directed to a polymerhaving a first type of repeating unit selected from crosslinkablerepeating units as described above and a second type of repeating unitselected from repeating units having a pendant silyl group, also asdescribed above. Polymers of this embodiment include polymers having afirst type of repeating unit selected from subformulae 34, 35, 36, 37and 38 (DMMIMeNB, DMMIEtNB, DMMIPrNB, DMMIBuNB, DMMIHxNB), and a secondtype of repeating unit selected from subformulae 53 and 54 (TMSNB,TESNB).

Another embodiment of the present invention is directed to a polymerhaving a first type of repeating unit selected from fluorinatedrepeating units as described above, a second type of repeating unitselected from crosslinkable repeating units, also as described above anda third type of repeating unit selected from polar repeating units,again as described above. Polymers of this embodiment include polymershaving a first repeating unit of subformula 9 (MeOAcNB), a second typeof repeating unit selected from subformulae 34, 35, 36, 37, or 38(DMMIMeNB, DMMIEtNB, DMMIPrNB, DMMIBuNB, DMMIHxNB), and a third type ofrepeating unit selected from subformula 16 (NBCH₂C₆F₅).

Another embodiment of the present invention is directed to a polymerhaving more than three different types of repeating units in accordancewith Formula I. Another embodiment of the present invention is directedto a polymer blend of a first polymer having a first type of repeatingunit in accordance with Formula I, and a second polymer having, atleast, a first type of repeating unit and a second type of repeatingunit in accordance with Formula I that is distinct from the first type.Alternatively such polymer blends can encompass the aforementionedsecond polymer mixed with an alternative first polymer having two ormore distinct types of repeat units in accordance with Formula I.Alternatively, such polymer blends can encompass the aforementionedalternative first polymer mixed with an alternative second polymerhaving three distinct types of repeat units in accordance with FormulaI.

Another embodiment of the present invention is directed to a polymerhaving a first and a second distinct type of repeat units in accordancewith Formula I where the ratio of such first and second type of repeatunits is from 95:5 to 5:95. In another embodiment the ratio of suchfirst and second type of repeat units is from 80:20 to 20:80. In stillanother embodiment the ratio of such first and second type of repeatunits is from 60:40 to 40:60. In yet another embodiment the ratio ofsuch first and second type of repeat units is from 55:45 to 45:55.

Another embodiment of the present invention encompasses a polymer blendof one or more polymers each having at least one type of repeat unit inaccordance with Formula I and one or more polymers having repeat unitsthat are different from norbornene-type repeat units. These otherpolymers are selected from polymers including but not limited topoly(methyl methacrylate) (PMMA), polystyrene (PS), poly-4-vinylphenol,polyvinylpyrrolidone, or combinations thereof, like PMMA-PS and-polyacrylonitrile (PAN).

Examples of suitable norbornene monomers, polymers and methods for theirsynthesis are provided herein and can also be found in U.S. Pat. No.5,468,819 B2, U.S. Pat. No. 6,538,087 B2, US 2006/0020068 A1, US2007/0066775 A1, US 2008/0194740 A1, PCT/EP2011/004281, U.S. Ser. No.13/223,784, PCT/EP2011/004282, U.S. Pat. No. 6,723,486 B2, U.S. Pat. No.6,455,650 B2 and U.S. Ser. No. 13/223,884, which are incorporated intothis application by reference. For example, exemplary polymerizationsprocesses employing Group VIII transition metal catalysts are describedin the aforementioned US 2006/0020068 A1.

The polymer embodiments of the present invention are formed having aweight average molecular weight (M_(w)) that is appropriate to theiruse. Generally, a M_(w) from 5,000 to 500,000 is found appropriate forsome embodiments, while for other embodiments other M_(w) ranges can beadvantageous. For example, in a embodiment, the polymer has a M_(w) ofat least 30,000, while in another embodiment the polymer has a M_(w) ofat least 60,000. In another embodiment, the upper limit of the polymer'sM_(w) is up to 400,000, while in another embodiment the upper limit ofthe polymer's M_(w) is up to 250,000. It will be understood that sincean appropriate M_(w) is a function of the desired physical properties inthe cured polymer, films, layers or structures derived therefrom, it isa design choice and thus any M_(w) within the ranges provided above iswithin the scope of the present invention.

In an embodiment of the present invention, a crosslinkable orcrosslinked polymer is used. It has been found that such a crosslinkableor crosslinked polymer can serve to improve one or more propertiesselected from structural integrity, durability, mechanical resistivityand solvent resistivity of the gate dielectric layer and the electronicdevice. Suitable crosslinkable polymers are for example those having oneor more repeating units of Formula I wherein one or more of R¹⁻⁴ denotesa crosslinkable group, units formed by monomers selected fromsubformulae 27-50.

For crosslinking, the polymer, generally after deposition thereof, isexposed to electron beam or electromagnetic (actinic) radiation such asX-ray, UV or visible radiation, or heated if it contains thermallycrosslinkable groups. For example, actinic radiation may be employed toimage-wise expose the polymer using a wavelength of from 11 nm to 700nm, such as from 200 to 700 nm. A dose of actinic radiation for exposureis generally from 25 to 15,000 mJ/cm². Suitable radiation sourcesinclude mercury, mercury/xenon, mercury/halogen and xenon lamps, argonor xenon laser sources, x-ray. Such exposure to actinic radiation causescrosslinking in exposed regions. Although other repeating unit pendantgroups that crosslink can be provided, generally such crosslinking isprovided by repeating units that encompass a maleimide pendant group,that is to say one of R¹ to R⁴ is a substituted or unsubstitutedmaleimide moiety. If it is desired to use a light source having awavelength outside of the photo-absorption band of the maleimide group,a radiation sensitive photosensitizer can be added. If the polymercontains thermally crosslinkable groups, optionally an initiator may beadded to initiate the crosslinking reaction, for example in case thecrosslinking reaction is not initiated thermally.

In one embodiment, the planarization layer is post exposure baked at atemperature from 70° C. to 130° C., for example for a period of from 1to 10 minutes. Post exposure bake can be used to further promotecrosslinking of crosslinkable moieties within exposed portions of thepolymer.

In another embodiment, the crosslinkable polymer composition comprises astabilizer material or moiety to prevent spontaneous crosslinking andimprove shelf life of the polymer composition. Suitable stabilizers areantioxidants such as catechol or phenol derivatives that optionallycontain one or more bulky alkyl groups, for example t-butyl groups, inortho-position to the phenolic OH group.

In order to improve the processing of the functional layers and theintegrity of the electronic device, it is desirable to decrease the timeneeded for the process while keeping or improving the physicalproperties of the layers being formed. This can be maintained wheresubsequent layers and solvents used in forming such layers areorthogonal and thus do not dissolve each other. Where such orthogonalityis difficult to obtain, crosslinking, typically UV crosslinking, a firstfunctional layer to make such first layer insoluble with respect to thepolymer composition of a second functional layer will prevent anyinfluence of the properties of either layer on the other layer.

Shortening the time needed for the processing can be done for example bytuning the coating process, while decreasing the time needed for UVcrosslinking can be achieved both by chemical adjustment of the polymeror by changes in the process.

However, chemical modifications of polymers are limited, because the UVsensitivity is related to certain properties of the polymer, and forexample changes towards increased UV sensitivity may decrease thesolubility. Changing the process, for example, by using higher power UV,could increase the possibility of creating an ozone atmosphere and thuscause undesired changes in the surface of the polymer.

Therefore, in some embodiments in accordance with the present inventionthe polymer composition comprises one or more crosslinker additives.Such additives comprise two or more functional groups that are capableof reacting with the pendant crosslinkable groups of thepolycycloolefinic polymer. It will also be understood that the use ofsuch crosslinker additives can also enhance the crosslinking of theaforementioned polymer.

In some embodiments in accordance with the present invention,crosslinking can be achieved by exposure to UV radiation.

The crosslinkable group of the crosslinker is selected from a maleimide,a 3-monoalkyl-maleimide, a 3,4-dialkylmaleimide, an epoxy, a vinyl, anacetylene, an indenyl, a cinnamate or a coumarin group, or a group thatcomprises a substituted or unsubstituted maleimide portion, an epoxideportion, a vinyl portion, an acetylene portion, an indenyl portion, acinnamate portion or a coumarin portion.

In some embodiments in accordance with the present invention, thecrosslinker is selected of formula III1 or III2

P-A″-X′-A″-P  III1

H_(4−c)C(A″-P)_(c)  III2

wherein X′ is O, S, NH or a single bond, A″ is a single bond or aconnecting, spacer or bridging group, which is for example selected from(CZ₂)_(n), (CH₂)_(n)—(CH═CH)_(p)—(CH₂)_(n), (CH₂)_(n)—O—(CH₂)_(n),(CH₂)_(n)—C₆Q₁₀-(CH₂)_(n), and C(O), where each n is independently aninteger from 0 to 12, p is an integer from 1-6, Z is independently H orF, C₆Q₁₀ is cyclohexyl that is substituted with Q, Q is independently H,F, CH₃, CF₃, or OCH₃, P is a crosslinkable group, and c is 2, 3, or 4,and where in formula III1 at least one of X′ and the two groups A″ isnot a single bond.

In one embodiment P is selected from a maleimide group, a3-monoalkyl-maleimide group, a 3,4-dialkylmaleimide group, an epoxygroup, a vinyl group, an acetylene group, an indenyl group, a cinnamategroup or a coumarin group, or comprises a substituted or unsubstitutedmaleimide portion, an epoxide portion, a vinyl portion, an acetyleneportion, an indenyl portion, a cinnamate portion or a coumarin portion.

Suitable compounds of formula III1 are selected from formula C1:

wherein R¹⁰ and R¹¹ are independently of each other H or a C₁-C₆ alkylgroup, and A″ is as defined in formula III1. In one embodiment of thisinvention, the crosslinkers are selected from DMMI-butyl-DMMI,DMMI-pentyl-DMMI and DMMI-hexyl-DMMI, wherein “DMMI” means3,4-dimethylmaleimide.

In one embodiment the spacer group A″ denotes linear C₁ to C₃₀ alkyleneor branched C₃ to C₃₀ alkylene or cyclic C₅ to C₃₀ alkylene, each ofwhich is unsubstituted or mono- or polysubstituted by F, Cl, Br, I, orCN, wherein optionally one or more non-adjacent CH₂ groups are replaced,in each case independently from one another, by —O—, —S—, —NH—, —NR¹⁸—,—SiR¹⁸R¹⁹—, —C(O)—, —C(O)O—, —OC(O)—, —OC(O)—O—, —S—C(O)—, —C(O)—S—,—CH═CH— or —C≡C— in such a manner that O and/or S atoms are not linkeddirectly to one another, R¹⁸ and R¹⁹ are independently of each other H,methyl, ethyl or a C₃ to C₁₂ linear or branched alkyl group.

Suitable groups A″ are —(CH₂)_(n)—, —(CH₂CH₂O)_(n)—, —CH₂CH₂—,—CH₂CH₂—S—CH₂CH₂— or —CH₂CH₂—NH—CH₂CH₂— or —(SiR¹⁸R¹⁹—O)_(n)—, with rbeing an integer from 2 to 12, s being 1, 2 or 3 and R¹⁸ and R¹⁹ havingthe meanings given above.

Further groups A″ are selected from methylene, ethylene, propylene,butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, octadecylene, ethyleneoxyethylene,methyleneoxybutylene, ethylene-thioethylene,ethylene-N-methyl-iminoethylene, 1-methylalkylene, ethenylene,propenylene, and butenylene.

The synthesis of crosslinkers like those of formula C1 is disclosed forexample in U.S. Pat. No. 3,622,321 which is incorporated by referenceinto this application.

The polymer compositions generally encompass, in addition to one or morepolymer components, a casting solvent optionally having orthogonalsolubility properties with respect to the insulating layer material andthe OSC layer, an optional cross-linking agent, an optional reactivesolvent, an optional UV sensitizer, and an optional thermal sensitizer.

In another embodiment the polymer composition used for preparation ofthe planarization layer comprises a crosslinkable polycycloolefinicpolymer and a reactive adhesion promoter. The reactive adhesion promotercomprises a first functional group that is capable of crosslinking withthe pendant crosslinkable group in the crosslinkable polycycloolefinicpolymer, and a second functional group which is a surface-active groupthat is capable of interactions, for example chemical bonding, with thefunctional layer provided onto the planarization layer. The adhesionpromoter may be used especially if the functional layer provided ontothe planarization layer is a semiconducting or dielectric layer.

Suitable adhesion promoters are selected of formula IV

G-A″-P  IV

wherein G is a surface-active group, preferably a silane or silazanegroup, A″ is a single bond or a connecting, spacer or bridging group,preferably as defined in formula III1 above, and P is a crosslinkablegroup, preferably as defined in formula III1 above.

In one embodiment G is a group of the formula —SiR¹²R¹³R¹⁴, or a groupof the formula —NH—SiR¹²R¹³R¹⁴, wherein R¹², R¹³ and R¹⁴ are eachindependently selected from halogen, silazane, C₁-C₁₂-alkoxy,C₁-C₁₂-alkylamino, optionally substituted C₅-C₂₀-aryloxy and optionallysubstituted C₂-C₂₀-heteroaryloxy, and wherein one or two of R¹², R¹³ andR¹⁴ may also denote C₁-C₁₂-alkyl, optionally substituted C₅-C₂₀-aryl oroptionally substituted C₂-C₂₀-heteroaryl.

In another embodiment P is selected from a maleimide, a3-monoalkyl-maleimide, a 3,4-dialkylmaleimide, an epoxy, a vinyl, anacetyl, an indenyl, a cinnamate or a coumarin group, or comprises asubstituted or unsubstituted maleimide portion, an epoxide portion, avinyl portion, an acetyl portion, an indenyl portion, a cinnamateportion or a coumarin portion.

In another embodiment A″ is selected from (CZ₂)_(n),(CH₂)_(n)—(CH═CH)_(p)—(CH₂)_(n), (CH₂)—O, (CH₂)_(n)—O—(CH₂)_(n),(CH₂)_(n)—C₆Q₄-(CH₂)_(n), (CH₂)_(n)—C₆Q₁₀-(CH₂)_(n) and C(O)—O, whereeach n is independently an integer from 0 to 12, p is an integer from1-6, Z is independently H or F, C₆Q₄ is phenyl that is substituted withQ, C₆Q₁₀ is cyclohexyl that is substituted with Q, Q is independently H,F, CH₃, CF₃ or OCH₃.

Suitable adhesion promoters are selected from formula A1:

where R¹², R¹³ R¹⁴, and A″ are as defined above, and R¹⁰ and R¹¹ areeach independently H or a C₁-C₆ alkyl group. Suitable compounds offormula A1 are for example DMMI-propyl-Si(OEt)₃, DMMI-butyl-Si(OEt)₃,DMMI-butyl-Si(OMe)₃, DMMI-hexyl-Si(OMe)₃, wherein “DMMI” means3,4-dimethylmaleimide.

The present invention also relates to an electronic device having orbeing obtained through the use of a polymer composition according to thepresent invention. Such electronic devices include, among others, fieldeffect transistors (FETs) and organic field effect transistors (OFETs),thin film transistors (TFT) and organic thin film transistors (OTFTs),which can be top gate or bottom gate transistors. For example,transistors made through the use of a polymer composition according tothe present invention are depicted schematically in FIGS. 3 and 4.

FIG. 1 and FIG. 2 depict schematic representations of top and bottomgate organic field effect transistors, respectively, according to priorart. Thus the OFET device of FIG. 1 and FIG. 2 include substrate (10),source and drain electrodes (20), organic semiconductor layer (30), gatedielectric layer (40), gate electrode (50), and an optional passivationlayer (60).

FIG. 3 is a schematic and exemplary representation of a top gate OFETdevice in accordance with one embodiment of the present invention. SuchOFET device includes substrate (10), planarization layer (70), which isderived from a polymer composition encompassing a polycycloolefinicpolymer or blend of polycycloolefinic polymer as described above andbelow, source and drain electrodes (20), organic semiconductor layer(30), gate electrode (50), gate dielectric layer (40), and optionallayer (60), which is for example a layer having one or more ofinsulating, protecting, stabilizing and adhesive function, and which isdisposed overlying gate electrode (50) and gate dielectric layer (40).

Another subject of the present invention is a process for preparing atop gate OFET device, for example as illustrated in FIG. 3, by a)depositing a layer of planarization material (70), which comprises apolycycloolefinic polymer or a polymer blend or polymer compositioncomprising a polycycloolefinic polymer as described above and below, ona substrate (10), b) forming source and drain electrodes (20) on atleast a portion of planarization layer (70) as depicted, c) depositing alayer of organic semiconductor material (30) over the previouslydeposited planarization layer (70) and source and drain electrodes (20),d) depositing a layer of dielectric material (40) on organicsemiconductor layer (30), e) forming gate electrode (50) on at least aportion of dielectric layer (40) as depicted, and f) optionallydepositing layer (60), which is for example an insulating and/orprotection and/or stabilizing and/or adhesive layer, on the gateelectrode (50) and portions of dielectric layer (40).

FIG. 4 is a schematic and exemplary representation of a bottom gate OFETdevice in accordance with an embodiment of the present invention. SuchOFET device includes substrate (10), planarization layer (70), which isderived from a polymer composition encompassing a polycycloolefinicpolymer or blend of polycycloolefinic polymer as described above andbelow, source and drain electrodes (20), organic semiconductor layer(30), gate electrode (50), gate dielectric layer (40), and optionalsecond insulator layer (60), which is a passivation or protection layerto shield the source and drain electrodes (20) from further layers ordevices provided on top of the device.

Another subject of the present invention is a process for preparing abottom gate OFET device, for example as illustrated in FIG. 4, by a)depositing a layer of planarization material (70), which comprises apolycycloolefinic polymer or a polymer blend or polymer compositioncomprising a polycycloolefinic polymer as described above and below, ona substrate (10), b) forming gate electrode (50) on at least a portionof planarization layer (70) as depicted, c) depositing a layer ofdielectric material (40) over the previously deposited planarizationlayer (70) and gate electrode (50), d) depositing a layer of organicsemiconductor material (30) on dielectric layer (40), e) forming sourceand drain electrodes (20) on at least a portion of organic semiconductorlayer (40) as depicted, and f) optionally depositing layer (60), whichis for example an insulating and/or protection and/or stabilizing and/oradhesive layer, on the source and drain electrodes (20) and portions oforganic semiconductor layer (30).

The aforementioned processes for preparing a transistor are anothersubject of the present invention.

Deposition and/or forming of the layers and structures of the OFETembodiments in accordance with the present invention are performed usingsolution processing techniques where such techniques are possible. Forexample a formulation or composition of a material, typically a solutionencompassing one or more organic solvents, can be deposited or formedusing techniques that include, but are not limited to, dip coating, spincoating, slot die coating, ink jet printing, letter-press printing,screen printing, doctor blade coating, roller printing, reverse-rollerprinting, offset lithography printing, flexographic printing, webprinting, spray coating, brush coating, or pad printing, followed by theevaporation of the solvent employed to form such a solution. Forexample, an organic semiconductor material and an organic dielectricmaterial can each be deposited or formed by spin coating, flexographicprinting, and inkjet printing techniques in an order appropriate to thedevice being formed. In one embodiment of this invention slot diecoating can be employed.

Specifically, where planarization layer (70) is deposited by solutionprocessing and employing a solution of one or more of the polymer orpolymer blends as described above and below in one or more organicsolvents, such solvents are preferably selected from, but not limitedto, organic ketones such as methyl ethyl ketone (MEK), 2-heptanone(MAK), cyclohexanone, cyclopentanone, and ethers such as butyl-phenylether, 4-methylanisole and aromatic hydrocarbons such ascyclohexylbenzene, or mixtures thereof. In one embodiment, the totalconcentration of the polymer material in the formulation is from 0.1-25wt. % although other concentrations can also be appropriate. Organicketone solvents with a high boiling point have been found to beespecially suitable and preferred solvents where inkjet and flexographicprinting techniques are employed.

The planarization layer (70) should be applied with an appropriatethickness to provide sufficient wetting and adhesion for any additionallayers coated thereon while not negatively affecting device performance.While the appropriate thickness of planarization layer (70) used infabricating a device is a function of the specific device being made andthe ultimate use of such a device, among other things, as generalguidelines it has been found that a preferred thickness in the range offrom 0.1 to 10 microns. It will be understood, however, that otherthickness ranges may be appropriate and thus are within the scope of thepresent invention.

In other embodiments of the present invention, a crosslinkable orcrosslinked polymer is used as the planarization layer material or as acomponent thereof. It has been found that such a crosslinkable orcrosslinked polymer can serve to improve one or more properties selectedfrom structural integrity, durability and solvent resistance of theplanarization layer and the electronic device. Very suitable andpreferred crosslinkable polymers are for example those having one ormore repeating units of Formula I wherein one or more of R¹⁻⁴ denotes acrosslinkable group, very preferably units of subformulae 27-50.

For crosslinking, the polymer, generally after deposition thereof, isexposed to electron beam or electromagnetic (actinic) radiation such asX-ray, UV or visible radiation, or heated if it contains thermallycrosslinkable groups. For example, actinic radiation may be employed toimage the polymer using a wavelength of from 11 nm to 700 nm, such asfrom 200 to 700 nm. A dose of actinic radiation for exposure isgenerally from 25 to 15,000 mJ/cm². Suitable radiation sources includemercury, mercury/xenon, mercury/halogen and xenon lamps, argon or xenonlaser sources, or X-ray. Such exposure to actinic radiation is to causecrosslinking in exposed regions. Although other repeating unit pendantgroups that crosslink can be provided, generally such crosslinking isprovided by repeating units that encompass a maleimide pendant group,that is to say one of R¹ to R⁴ is a substituted or unsubstitutedmaleimide moiety. If it is desired to use a light source having awavelength outside of the photo-absorption band of the maleimide group,a radiation sensitive photosensitizer can be added. If the polymercontains thermally crosslinkable groups, optionally an initiator may beadded to initiate the crosslinking reaction, for example in case thecrosslinking reaction is not initiated thermally.

In an embodiment, the planarization layer is post exposure baked at atemperature from 70° C. to 130° C., for example for a period of from 1to 10 minutes. Post exposure bake can be used to further promotecrosslinking of crosslinkable moieties within exposed portions of thepolymer.

The other components or functional layers of the electronic device, likethe substrate, the gate and source and drain electrodes, and organicsemiconductor layer, can be selected from standard materials, and can bemanufactured and applied to the device by standard methods. Suitablematerials and manufacturing methods for these components and layers areknown to a person skilled in the art and are described in theliterature. Exemplary deposition methods include the liquid coatingmethods previously described as well as chemical vapor deposition (CVD)or physical vapor deposition methodologies.

Generally the thickness of a functional layer, for example a gatedielectric or organic semiconductor layer, in some electronic deviceembodiments according to the present invention is from 0.001 (in case ofa monolayer) to 10 μm; In other embodiments such thickness ranges from0.001 nm to 1 μm, and in still other embodiments from 5 nm to 500 nm,although other thicknesses or ranges of thickness are contemplated andthus are within the scope of the present invention.

Various substrates may be used for the fabrication of the electronicdevice embodiments of the present invention. For example glass orpolymeric materials are most often used. In other embodiments, polymericmaterials include, but are not limited to, alkyd resins, allyl esters,benzocyclobutenes, butadiene-styrene, cellulose, cellulose acetate,epoxy polymers, ethylene-chlorotrifluoro ethylene copolymers,ethylene-tetra-fluoroethylene copolymers, fiber glass enhancedthermoplastic, fluorocarbon polymers,hexafluoropropylenevinylidene-fluoride copolymer, polyethylene,parylene, polyamide, polyimide, polyaramid, polydimethylsiloxane,polyethersulphone, polyethylenenaphthalate, polyethyleneterephthalate,polyketone, polymethylmethacrylate, polypropylene, polystyrene,polysulphone, polytetrafluoroethylene, polyurethanes, polyvinylchloride,polycycloolefin, silicone rubbers, and silicones, wherepolyethyleneterephthalate, polyimide, polycycloolefin andpolyethylenenaphthalate materials have been found most appropriate.Additionally, for some embodiments of the present invention thesubstrate can be any thermoplastic, metal or glass material coated withone or more of the above listed materials.

In one embodiment, the substrate is a polymer film of a polymer selectedfrom the group consisting of polyesters, polyimides, polyarylates,polycycloolefins, polycarbonates and polyethersulphones.

In other embodiments, polyester substrates, most preferably polyethyleneterephthalate (PET) or polyethylene naphthalate (PEN), for example PETfilms of the Melinex® series or PEN films of the Teonex® series, bothfrom DuPont Teijin Films™ may be used.

The gate, source and drain electrodes of the OFET device embodiments inaccordance with the present invention can be deposited or formed byliquid coating, such as spray-, dip-, web- or spin-coating, or by vacuumdeposition methods, including but not limited to physical vapordeposition (PVD), chemical vapor deposition (CVD) or thermalevaporation. Suitable electrode materials and deposition methods areknown to the person skilled in the art. Suitable electrode materialsinclude, without limitation, inorganic or organic materials, orcomposites of the two. Exemplary electrode materials includepolyaniline, polypyrrole, poly(3,4-ethylene-dioxythiophene) (PEDOT) ordoped conjugated polymers, further dispersions or pastes of graphite orgraphene or particles of metal such as Au, Ag, Cu, Al, Ni or theirmixtures as well as sputter coated or evaporated metals such as Cu, Cr,Pt/Pd, Ag, Au or metal oxides such as indium tin oxide (ITO), F-dopedITO or Al-doped ZnO. Organometallic precursors may also be used anddeposited from a liquid phase.

The organic semiconductor materials and methods for applying the organicsemiconductor layer for OFET embodiments in accordance with the presentinvention can be selected from standard materials and methods known tothe person skilled in the art, and are described in the literature. Theorganic semiconductor can be an n- or p-type OSC, which can be depositedby PVD, CVD or solution deposition methods. Effective OSCs exhibit a FETmobility of greater than 1×10⁻⁵ cm²V⁻¹s⁻¹.

OSC embodiments in accordance with the present invention can be eitherOFETs where the OSC is used as the active channel material, OPV deviceswhere the OSC is used as charge carrier material, or organic rectifyingdiodes (ORDs) where the OSC is a layer element of such a diode. OSCs forsuch embodiments can be deposited by any of the previously discusseddeposition methods, but as they are generally deposited or formed asblanket layers, solvent coated methods such as spray-, dip-, web- orspin-coating, or printing methods such as ink-jet printing, flexoprinting or gravure printing, are typically employed to allow forambient temperature processing. However, OSCs can be deposited by anyliquid coating technique, for example ink-jet deposition or via PVD orCVD techniques.

For some OFET embodiments, the semiconducting layer that is formed canbe a composite of two or more of the same or different types of organicsemiconductors. For example, a p-type OSC material may, for example, bemixed with an n-type material to achieve a doping effect of the layer.In some embodiments of the invention, multilayer organic semiconductorlayers are used. For example an intrinsic organic semiconductor layercan be deposited near the gate dielectric interface and a highly dopedregion can additionally be coated adjacent to such an intrinsic layer.

The OSC material employed for electronic device embodiments inaccordance with the present invention can be any conjugated molecule,for example an aromatic molecule containing preferably two or more, verypreferably at least three aromatic rings. In some embodiments of thepresent invention, the OSC contains aromatic rings selected from 5-, 6-or 7-membered aromatic rings, while in other embodiments the OSCcontains aromatic rings selected from 5- or 6-membered aromatic rings.The OSC material may be a monomer, oligomer or polymer, includingmixtures, dispersions and blends of one or more of monomers, oligomersor polymers.

Each of the aromatic rings of the OSC optionally contains one or morehetero atoms selected from Se, Te, P, Si, B, As, N, O or S, generallyfrom N, O or S. Further, the aromatic rings may be optionallysubstituted with alkyl, alkoxy, polyalkoxy, thioalkyl, acyl, aryl orsubstituted aryl groups, halogen, where fluorine, cyano, nitro or anoptionally substituted secondary or tertiary alkylamine or arylaminerepresented by —N(R¹⁵)(R¹⁶), where R¹⁵ and R¹⁶ are each independently H,an optionally substituted alkyl or an optionally substituted aryl,alkoxy or polyalkoxy groups are typically employed. Further, where R¹⁵and R¹⁶ is alkyl or aryl these may be optionally fluorinated.

The aforementioned aromatic rings can be fused rings or linked with aconjugated linking group such as —C(T₁)=C(T₂)-, —C≡C—, —N(R′″)—, —N═N—,(R′″)═N—, —N═C(R′″)—, where T₁ and T₂ each independently represent H,Cl, F, —C≡N or lower alkyl groups such as C₁₋₄ alkyl groups; R′″represents H, optionally substituted alkyl or optionally substitutedaryl. Further, where R′″ is alkyl or aryl can be fluorinated.

In some preferred electronic device embodiments of the presentinvention, OSC materials that can be used include compounds, oligomersand derivatives of compounds selected from the group consisting ofconjugated hydrocarbon polymers such as polyacene, polyphenylene,poly(phenylene vinylene), polyfluorene including oligomers of thoseconjugated hydrocarbon polymers; condensed aromatic hydrocarbons, suchas, tetracene, chrysene, pentacene, pyrene, perylene, coronene, orsoluble, substituted derivatives of these; oligomeric para substitutedphenylenes such as p-quaterphenyl (p-4P), p-quinquephenyl (p-5P),p-sexiphenyl (p-6P), or soluble substituted derivatives of these;conjugated heterocyclic polymers such as poly(3-substituted thiophene),poly(3,4-bisubstituted thiophene), optionally substitutedpolythieno[2,3-b]thiophene, optionally substitutedpolythieno[3,2-b]thiophene, poly(3-substituted selenophene),polybenzothiophene, polyisothianapthene, poly(N-substituted pyrrole),poly(3-substituted pyrrole), poly(3,4-bisubstituted pyrrole), polyfuran,polypyridine, poly-1,3,4-oxadiazoles, polyisothianaphthene,poly(N-substituted aniline), poly(2-substituted aniline),poly(3-substituted aniline), poly(2,3-bisubstituted aniline),polyazulene, polypyrene; pyrazoline compounds; polyselenophene;polybenzofuran; polyindole; polypyridazine; benzidine compounds;stilbene compounds; triazines; substituted metallo- or metal-freeporphines, phthalocyanines, fluorophthalocyanines, naphthalocyanines orfluoronaphthalocyanines; C₆₀ and C₇₀ fullerenes; N,N′-dialkyl,substituted dialkyl, diaryl or substituteddiaryl-1,4,5,8-naphthalenetetracarboxylic diimide and fluoroderivatives; N,N′-dialkyl, substituted dialkyl, diaryl or substituteddiaryl 3,4,9,10-perylenetetracarboxylicdiimide; bathophenanthroline;diphenoquinones; 1,3,4-oxadiazoles;11,11,12,12-tetracyanonaptho-2,6-quinodimethane;α,α′-bis(dithieno[3,2-b2′,3′-d]thiophene); 2,8-dialkyl, substituteddialkyl, diaryl or substituted diaryl anthradithiophene;2,2′-bibenzo[1,2-b:4,5-b′]dithiophene. Where a liquid depositiontechnique of the OSC is desired, compounds from the above list andderivatives thereof are limited to those that are soluble in anappropriate solvent or mixture of appropriate solvents.

Further, in some embodiments in accordance with the present invention,the OSC materials are polymers or copolymers that encompass one or morerepeating units selected from thiophene-2,5-diyl, 3-substitutedthiophene-2,5-diyl, optionally substitutedthieno[2,3-b]thiophene-2,5-diyl, optionally substitutedthieno[3,2-b]thiophene-2,5-diyl, selenophene-2,5-diyl, or 3-substitutedselenophene-2,5-diyl.

Further p-type OSCs are copolymers comprising electron acceptor andelectron donor units. Copolymers of this embodiment are for examplecopolymers comprising one or morebenzo[1,2-b:4,5-b′]dithiophene-2,5-diyl units that are 4,8-disubstitutedby one or more groups R as defined above, and further comprising one ormore aryl or heteroaryl units selected from Group A and Group B,comprising at least one unit of Group A and at least one unit of GroupB, wherein Group A consists of aryl or heteroaryl groups having electrondonor properties and Group B consists of aryl or heteroaryl groupshaving electron acceptor properties, and Group A consists ofselenophene-2,5-diyl, thiophene-2,5-diyl,thieno[3,2-b]thiophene-2,5-diyl, thieno[2,3-b]thiophene-2,5-diyl,selenopheno[3,2-b]selenophene-2,5-diyl,selenopheno[2,3-b]selenophene-2,5-diyl,selenopheno[3,2-b]thiophene-2,5-diyl,selenopheno[2,3-b]thiophene-2,5-diyl, benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl, 2,2-dithiophene, 2,2-diselenophene,dithieno[3,2-b:2′,3′-d]silole-5,5-diyl,4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl,2,7-di-thien-2-yl-carbazole, 2,7-di-thien-2-yl-fluorene,indaceno[1,2-b:5,6-b′]dithiophene-2,7-diyl,benzo[1″,2″:4,5;4″,5″:4′,5′]bis(silolo[3,2-b:3′,2′-b′]thiophene)-2,7-diyl,2,7-di-thien-2-yl-indaceno[1,2-b:5,6-b′]dithiophene,2,7-di-thien-2-yl-benzo[1″,2″:4,5;4″,5″:4′,5′]bis(silolo[3,2-b:3′,2′-b′]thiophene)-2,7-diyl,and 2,7-di-thien-2-yl-phenanthro[1,10,9,8-c,d,e,f,g]carbazole, all ofwhich are optionally substituted by one or more, one or two groups R asdefined above, and Group B consists of benzo[2,1,3]thiadiazole-4,7-diyl,5,6-dialkyl-benzo[2,1,3]thiadiazole-4,7-diyl,5,6-dialkoxybenzo[2,1,3]thiadiazole-4,7-diyl,benzo[2,1,3]selenadiazole-4,7-diyl,5,6-dialkoxy-benzo[2,1,3]selenadiazole-4,7-diyl,benzo[1,2,5]thiadiazole-4,7,diyl, benzo[1,2,5]selenadiazole-4,7,diyl,benzo[2,1,3]oxadiazole-4,7-diyl,5,6-dialkoxybenzo[2,1,3]oxadiazole-4,7-diyl, 2H-benzotriazole-4,7-diyl,2,3-dicyano-1,4-phenylene, 2,5-dicyano, 1,4-phenylene,2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene,2,3,5,6-tetrafluoro-1,4-phenylene, 3,4-difluorothiophene-2,5-diyl,thieno[3,4-b]pyrazine-2,5-diyl, quinoxaline-5,8-diyl,thieno[3,4-b]thiophene-4,6-diyl, thieno[3,4-b]thiophene-6,4-diyl,3,6-pyrrolo[3,4-c]pyrrole-1,4-dione, all of which are optionallysubstituted by one or more, preferably one or two groups R as definedabove.

In other embodiments of the present invention, the OSC materials aresubstituted oligoacenes such as pentacene, tetracene or anthracene, orheterocyclic derivatives thereof. Bis(trialkylsilylethynyl)oligoacenesor bis(trialkylsilylethynyl)heteroacenes, as disclosed for example inU.S. Pat. No. 6,690,029 or WO 2005/055248 A1 or U.S. Pat. No. 7,385,221,are incorporated by reference into this application, are also useful.

Where appropriate and needed to adjust the rheological properties asdescribed for example in WO 2005/055248 A1, some embodiments of thepresent invention employ OSC compositions that include one or moreorganic binders.

The binder, which is typically a polymer, may comprise either aninsulating binder or a semiconducting binder, or mixtures thereof may bereferred to herein as the organic binder, the polymeric binder, orsimply the binder.

Preferred binders according to the present invention are materials oflow permittivity, that is, those having a permittivity c of 3.3 or less.The organic binder preferably has a permittivity c of 3.0 or less, morepreferably 2.9 or less. Preferably the organic binder has a permittivityc at of 1.7 or more. It is especially preferred that the permittivity ofthe binder is in the range from 2.0 to 2.9. Whilst not wishing to bebound by any particular theory it is believed that the use of binderswith a permittivity c of greater than 3.3, may lead to a reduction inthe OSC layer mobility in an electronic device, for example an OFET. Inaddition, high permittivity binders could also result in increasedcurrent hysteresis of the device, which is undesirable.

Examples of a suitable organic binders include polystyrene, or polymersor copolymers of styrene and α-methyl styrene, or copolymers includingstyrene, α-methylstyrene and butadiene may suitably be used. Furtherexamples of suitable binders are disclosed for example in US2007/0102696 A1 is incorporated by reference into this application.

In one type of embodiment, the organic binder is one in which at least95%, in an other embodiment at least 98% and another embodiment when allof the atoms consist of hydrogen, fluorine and carbon atoms.

The binder is preferably capable of forming a film, more preferably aflexible film.

The binder can also be selected from crosslinkable binders, such asacrylates, epoxies, vinylethers, and thiolenes, preferably having asufficiently low permittivity, very preferably of 3.3 or less. Thebinder can also be mesogenic or liquid crystalline.

In another embodiment the binder is a semiconducting binder, whichcontains conjugated bonds, especially conjugated double bonds and/oraromatic rings. Suitable and preferred binders are for examplepolytriarylamines as disclosed for example in U.S. Pat. No. 6,630,566.

The proportions of binder to OSC is typically 20:1 to 1:20 by weight,preferably 10:1 to 1:10 more preferably 5:1 to 1:5, still morepreferably 3:1 to 1:3 further preferably 2:1 to 1:2 and especially 1:1.Dilution of the compound of formula I in the binder has been found tohave little or no detrimental effect on the charge mobility, in contrastto what would have been expected from the prior art.

Unless the context clearly indicates otherwise, as used herein pluralforms of the terms herein are to be construed as including the singularform and vice versa.

It will be appreciated that variations to the foregoing embodiments ofthe invention can be made while still falling within the scope of theinvention. Each feature disclosed in this specification, unless statedotherwise, may be replaced by alternative features serving the same,equivalent or similar purpose. Thus, unless stated otherwise, eachfeature disclosed is one example only of a generic series of equivalentor similar features.

All of the features disclosed in this specification may be combined inany combination, except combinations where at least some of suchfeatures and/or steps are mutually exclusive. In particular, thefeatures of the invention are applicable to all aspects of the inventionand may be used in any combination. Likewise, features described innon-essential combinations may be used separately (not in combination).

The invention will now be described in more detail by reference to thefollowing examples, which are illustrative only and do not limit thescope of the invention.

Above and below, unless stated otherwise percentages are percent byweight and temperatures are given in degrees Celsius (° C.). The valuesof the dielectric constant ∈ (“permittivity”) refer to values taken at1,000 Hz and 20° C.

Unless stated otherwise, the values of the surface energy refer to thosecalculated from contact angle measurement of the polymers according tothe method described in D. K. Owens, R. C. Wendt, “Estimation of thesurface free energy of polymers”, Journal of Applied Polymer Science,Vol. 13, 1741-1747, 1969 or “Surface and Interfacial Tension:Measurement, Theory, and Applications (Surfactant Science Series Volume119)” by Stanley Hartland (Editor), Taylor & Francis Ltd; 2004 (ISBN:0-8247-5034-9), chapter 7, p.: 375: “Contact Angle and Surface TensionMeasurement” by Kenji Katoh).

Comparison Example 1 Top Gate OFET with Teonex® PEN Film as Substrate

Teonex Q65FA® PEN film (available from DuPont Teijin Films™) was washedin methanol and treated with argon plasma for 3 min (microwave plasmagenerator, power: 100 W, argon flow: 500 ml/min) in order to increasesurface energy of the substrate.

60 nm thick gold source drain electrodes were evaporated directly ontothe PEN substrate with a parallel plate geometry of 20 μm wide by 1 mmlong.

The electrodes were treated with Lisicon M001® (available from MerckChemicals Ltd.) by spin coating from isopropyl alcohol and evaporatingthe excess off on a hot plate at 70° C. for 2 min.

An OSC Lisicon S1200-Series® formulation was used (available from MerckChemicals Ltd.).

The OSC formulation was then printed as a 5×5 cm wide area block on thearray of source/drain electrodes on the film as described above using aRK Flexiproof 100 flexographic printing with a 8 cm³/m² loaded aniloxand a Cyrel HiQS flexo mat running at 70 m/min speed. The printed OSClayer was then annealed at 70° C. for 5 min.

A dielectric layer of fluoro-polymer Lisicon D139® (9% solids availablefrom Merck Chemicals Ltd.) was spun on top of the OSC layer on thedevice and annealed at 70° C. for 8 min to give a dry dielectric film ofapproximately 1 μm thick.

Finally a 40 nm thick gold gate electrode array of evaporated on top ofthe dielectric layer in such a way that it covered the existing sourcedrain electrode structures.

The initial transfer curve was recorder at bias voltage of −5 V. Thenthe device was electrically stressed for 15 h using source/gate voltageof −40 V and the second transfer curve was recorded directly after thestress.

The transfer characteristics are shown in FIG. 5.

Example 1 Top Gate OFET with a Teonex® Film Covered by a PolynorbornenePlanarization Layer According to the Invention as Substrate

Teonex Q65FA® film (available from DuPont Teijin Films™) was washed inmethanol. A layer of the polymer poly(DMMIBuNB) (hereinafter abbreviatedas “pDMMIBuNB”), which is a homopolymer of the monomer of formula (37),having a molecular weight M_(W)=100,000, was formed by depositing asolution of the polymer (17.5% TS in MAK with added 0.5%1-chloro-4-propoxy-9H-thioxanthen-9-one w/w) onto the Teonex film viaspin coating (1500 rpm, 30 s) followed by 8 min baking at 70° C. and 4min UV exposure (UVA 0.011W/cm², peak at 365 nm).

Approximately 60 nm thick gold source drain electrodes were evaporatedonto the polynorbornene layer with a parallel plate geometry of 20 μmwide by 1 mm long.

The electrodes were treated with M001 (available from Merck ChemicalsLtd.) by spin coating from isopropyl alcohol and evaporating the excessoff on a hot plate at 70° C. for 2 min.

The same OSC Lisicon S1200-Series® formulation as used in ComparisonExample 1 was then printed as a 5×5 cm wide area block on the array ofsource/drain electrodes on the film as described above using a RKFlexiproof 100 flexographic printing with a 8 cm³/m² loaded anilox and aCyrel HiQS flexo mat running at 70 m/min speed. The printed OSC layerwas then annealed at 70° C. for 5 min.

A dielectric layer of fluoro-polymer Lisicon D139® (9% solids availablefrom Merck Chemicals Ltd.) was spun on top of the OSC layer on thedevice and annealed at 70° C. for 8 min to give a dry dielectric filmapproximately 1 μm thick.

Finally a 40 nm thick gold gate electrode array is evaporated on top ofthe dielectric layer in such a way that it covered the existing sourcedrain electrode structures.

The initial transfer curve was recorder at bias voltage of −5 V. Thenthe device was electrically stressed for 15 h using source/gate voltageof −40 V and the second transfer curve was recorded directly after thestress.

The transfer characteristics are shown in FIG. 6.

From FIG. 6 it can be seen that in the OFET device of Example 1, thelayer of pDMMIBuNB on top of Teonex Q65FA® film improves stability ofthe electrical parameters, in comparison to the OFET device ofComparison Example 1 without the additional pDMMIBuNB layer (see FIG.5). Stability of the source-drain current in the ‘ON’ state (undernegative gate bias in case of using p-type semiconductors) and limitedthreshold voltage shift after application of negative gate bias stress(−40 V) are particularly important to ensure applicability of thetransistors.

Such an improved long term stability of those parameters was observedfor the devices containing the planarization layer of pDMMIBuNB,compared to devices without the layer of pDMMIBuNB.

The surface roughness of the substrates of Comparison Example 1 andExample 1 was measured by Atomic Force Microscopy (AFM).

As a result the surface roughness of the Teonex Q65FA® substrate as usedin Comparison Example 1 is 0.6 nm (Ra) and 20 nm (Rt), whereas thesurface roughness of the same substrate coated with a layer of pDMMIBuNBas used in Example 1, is 0.2 nm (Ra) and 5 nm (Rt) for pDMMIBuNB layer.

This shows that the surface roughness was significantly reduced afterapplication of the planarization layer of pDMMIBuNB.

Surface energy measurements using the Owens-Wendt method were carriedout for the substrates of Comparison Example 1 and Example 1.

As a result the surface energy of the Teonex Q65FA® substrate as used inComparison Example 1 is 32 mN/m (without plasma treatment), whereas thesurface energy of the same substrate coated with a layer of pDMMIBuNB asused in Example 1, is 50 mN/m respectively.

Since de-wetting may occur at low surface energies<40 mN/m, thesubstrate of Comparison Example 1 needs further plasma treatment toincrease surface energy. In contrast thereto, a surface modification ofthe pDMMIBuNB layer prior to the OSC deposition, for example in order toimprove surface energy and wetting, is not required. Nevertheless,pDMMIBuNB is resistant to plasma treatment, which is commonly appliedafter a photolithographic process in order to remove post-processresidues.

Comparison Example 2 Top Gate OFET with Melinex® Film as Substrate

Melinex ST506® film (available from DuPont Teijin Films™) was washed inmethanol and treated with argon plasma for 3 min (microwave plasmagenerator, power: 100 W, argon flow: 500 ml/min) in order to increasesurface energy of the substrate.

Approximately 60 nm thick gold source drain electrodes were evaporatedonto the directly onto the PEN substrate layer with a parallel plategeometry of 20 μm wide by 1 mm long.

The electrodes were treated with Lisicon M001® (available from MerckChemicals Ltd.) by spin coating from isopropyl alcohol and evaporatingthe excess off on a hot plate at 70° C. for 2 min.

The same OSC Lisicon S1200-Series® formulation as used in ComparisonExample 1 was then printed as a 5×5 cm wide area block on the array ofsource/drain electrodes on the film as described above using a RKFlexiproof 100 flexographic printing with a 8 cm³/m² loaded anilox and aCyrel HiQS flexo mat running at 70 m/min speed. The printed OSC layerwas then annealed at 70° C. for 5 min.

A dielectric layer of fluoro-polymer Lisicon D139® (9% solids availablefrom Merck Chemicals Ltd.) was spun on top of the OSC layer on thedevice and annealed at 70° C. for 8 min to give a dry dielectric film ofapproximately 1 μm thick.

Finally a 40 nm thick gold gate electrode array is evaporated on top ofthe dielectric layer in such a way that it covered the existing sourcedrain electrode structures.

The initial transfer curve was recorder at bias voltage of −5 V. Thenthe device was electrically stressed for 2 h using source/gate voltageof 30 V and the second transfer curve was recorded directly after thestress.

The transfer characteristics are shown in FIG. 7.

Example 2 Top Gate OFET Device with a Melinex® Film Covered by aPolynorbornene Planarization Layer According to the Invention asSubstrate

Melinex ST506® film (available from DuPont Teijin Films™) was washed inmethanol. A layer of the norbornene polymer pBuDMMINB (17.5% TS in MAKwith added 0.5% 1-chloro-4-propoxy-9H-thioxanthen-9-one w/w) wasdeposited onto the Melinex film via spin coating (1500 rpm, 30 s)followed by 8 min baking at 70° C. and 4 min UV exposure (UVA0.011W/cm2, peak at 365 nm).

Approximately 60 nm thick gold source drain electrodes were evaporatedonto the polynorbornene layer with a parallel plate geometry of 20 μmwide by 1 mm long.

The electrodes were treated with Lisicon M001® (available from MerckChemicals Ltd.) by spin coating from isopropyl alcohol and evaporatingthe excess off on a hot plate at 70° C. for 2 min.

The same OSC Lisicon S1200-Series® formulation as used in ComparisonExample 1 was then printed as a 5×5 cm wide area block on the array ofsource/drain electrodes on the film as described above using a RKFlexiproof 100 flexographic printing with a 8 cm³/m² loaded anilox and aCyrel HiQS flexo mat running at 70 m/min speed. The printed OSC layerwas then annealed at 70° C. for 5 min.

A dielectric layer of fluoro-polymer Lisicon D139® (9% solids availablefrom Merck Chemicals Ltd.) was spun on top of the OSC layer on thedevice and annealed at 70° C. for 8 min to give a dry dielectric film ofapproximately 1 μm thick.

Finally a 40 nm thick gold gate electrode array is evaporated on top ofthe dielectric layer in such a way that it covered the existing sourcedrain electrode structures.

The initial transfer curve was recorder at bias voltage of −5 V. Thenthe device was electrically stressed for 80 h using source/gate voltageof 30 V and the second transfer curve was recorded directly after thestress.

The transfer characteristics are shown in FIG. 8.

From FIG. 8 it can be seen that in the OFET device of Example 2, thelayer of pDMMIBuNB on top of Melinex ST506® film improves stability ofthe electrical parameters, in comparison to the OFET device ofComparison Example 2 without the additional pDMMIBuNB layer (see FIG.7). Stability of the source-drain current in the ‘ON’ state (undernegative gate bias in case of using p-type semiconductors) and limitedthreshold voltage shift after application of positive gate bias stress(30V) are particularly important to ensure applicability of thetransistors.

Such an improved long term stability of those parameters was observedfor the devices containing the planarization layer of pDMMIBuNB,compared to devices without the layer of pDMMIBuNB.

The surface roughness of the substrates of Comparison Example 2 andExample 2 was measured by Atomic Force Microscope.

As a result the surface roughness of the Melinex ST506® substrate asused in Comparison Example 2 is 0.6 nm (R_(a)) and 20 nm (R_(t)),whereas the surface roughness of the same substrate coated with a layerof pDMMIBuNB as used in Example 2, is 0.2 nm (R_(a)) and 5 nm (R_(t))for pDMMIBuNB layer.

This shows that the surface roughness was significantly reduced afterapplication of the planarization layer of pDMMIBuNB.

Surface energy measurements using the Owens-Wendt method were carriedout for the substrates of Comparison Example 2 and Example 2.

As a result the surface energy of the Melinex ST506® substrate as usedin Comparison Example 2 is 33 mN/m, whereas the surface energy of thesame substrate coated with a layer of pDMMIBuNB as used in Example 2, is50 mN/m respectively.

Since de-wetting may occur at low surface energies<40 mN/m, thesubstrate of Comparison Example 2 needs further plasma treatment toincrease surface energy. In contrast thereto, a surface modification ofthe pDMMIBuNB layer prior to the OSC deposition, for example in order toimprove surface energy and wetting, is not required. Nevertheless,pDMMIBuNB is resistant to plasma treatment, which is commonly appliedafter a photolithographic process in order to remove post-processresidues.

The adhesion of Au gold to the substrates of Comparison Example 2 andExample 2 was measured by Mecmesin MultiTest 1-i (50 N cell) using 90°peel test. For that purpose both substrates were covered byapproximately 60 nm layers of gold and 25 mm wide tape with 20 Nadhesion to gold was applied to peel a stripe of gold from thesubstrates.

As a result the adhesion of gold to the Melinex ST506® substrate as usedin Comparison Example 2 is less or equal to 0.5N whereas the adhesion ofgold to the same substrate coated with a layer of pDMMIBuNB as used inExample 2, is 16 N.

Example 3 Top Gate OFET Device with a Melinex® Film Covered by aPolynorbornene Planarization Layer According to the Invention asSubstrate

Melinex ST506® film (available from DuPont Teijin Films™) was washed inmethanol. A layer of the norbornene polymer poly(DMMIBuNB/TESNB) whichis a co-polymer of the monomer DMMIBuNB of the formula (37) and themonomer TESNB of the formula (53) in the ratio: 9:1, dissolved in MAK tothe concentration of 17.5% TS) was deposited onto the Melinex film viaspin coating (1500 rpm, 30 s) followed by 8 min baking at 70° C. and 5min UV exposure (UVA 0.011W/cm², peak at 365 nm).

Approximately 60 nm thick gold source drain electrodes were evaporatedonto the polynorbornene layer with a parallel plate geometry of 20 μmwide by 1 mm long.

The electrodes were treated with Lisicon M001® (available from MerckChemicals Ltd.) by spin coating from isopropyl alcohol and evaporatingthe excess off on a hot plate at 70° C. for 2 min.

The same OSC Lisicon S1200-Series® formulation as used in ComparisonExample 1 was then printed as a 5×5 cm wide area block on the array ofsource/drain electrodes on the film as described above using a RKFlexiproof 100 flexographic printing with a 8 cm³/m² loaded anilox and aCyrel HiQS flexo mat running at 70 m/min speed. The printed OSC layerwas then annealed at 70° C. for 5 min.

A dielectric layer of fluoro-polymer Lisicon D139® (9% solids availablefrom Merck Chemicals Ltd.) was spun on top of the OSC layer on thedevice and annealed at 70° C. for 8 min to give a dry dielectric film ofapproximately 1 μm thick.

Finally a 40 nm thick gold gate electrode array is evaporated on top ofthe dielectric layer in such a way that it covered the existing sourcedrain electrode structures.

The initial transfer curve was recorder at bias voltage of −5 V. Thenthe device was electrically stressed for 80 h using source/gate voltageof 30 V and the second transfer curve was recorded directly after thestress.

The transfer characteristics are shown in FIG. 9.

From FIG. 9 it can be seen that in the OFET device of Example 3, thelayer of poly(DMMIBuNB/TESNB) on top of Melinex ST506® film improvesstability of the electrical parameters, in comparison to the OFET deviceof Comparison Example 3 without the additional poly(DMMIBuNB/TESNB)layer (see FIG. 7). Stability of the source-drain current in the ‘ON’state (under negative gate bias in case of using p-type semiconductors)and limited threshold voltage shift after application of positive gatebias stress (30V) are particularly important to ensure applicability ofthe transistors.

Such an improved long term stability of those parameters was observedfor the devices containing the planarization layer ofpoly(DMMIBuNB/TESNB), compared to devices without the layer ofpoly(DMMIBuNB/TESNB).

Furthermore, the OFET device of Example 3 shows a decreased source-draincurrent in the ‘OFF’ state (under positive gate bias in case of usingp-type semiconductors) by over one order of magnitude for non-patternedOSC layer (where OSC layer covers the whole area of a substrate andthere is significant current leakage between the neighbouring devicesthrough the OSC layer).

The surface roughness of the substrates of Comparison Example 2 andExample 3 was measured by Atomic Force Microscopy.

As a result the surface roughness of the Melinex ST506® substrate asused in Comparison Example 2 (without plasma treatment) is 0.6 nm(R_(a)) and 20 nm (R_(t)), whereas the surface roughness of the samesubstrate coated with a layer of poly(DMMIBuNB/TESNB) as used in Example3, is 0.2 nm (R_(a)) and 5 nm (R_(t)) for poly(DMMIBuNB/TESNB) layer.

This shows that the surface roughness was significantly reduced afterapplication of the planarization layer of poly(DMMIBuNB/TESNB).

Surface energy measurements using the Owens-Wendt method were carriedout for the substrates of Comparison Example 2 and Example 3.

As a result the surface energy of the Melinex ST506® substrate as usedin Comparison Example 2 is 33 mN/m, whereas the surface energy of thesame substrate coated with a layer of poly(DMMIBuNB/TESNB) as used inExample 3, is 51 mN/m respectively.

Since de-wetting may occur at low surface energies<40 mN/m, thesubstrate of Comparison Example 2 needs further plasma treatment toincrease surface energy. In contrast thereto, a surface modification ofthe poly(DMMIBuNB/TESNB) layer prior to the OSC deposition, for examplein order to improve surface energy and wetting, is not required.Nevertheless, poly(DMMIBuNB/TESNB) is resistant to plasma treatment,which is commonly applied after a photolithographic process in order toremove post-process residues.

The adhesion of Au gold to the substrates of Comparison Example 2 andExample 3 was measured by Mecmesin MultiTest 1-i (50 N cell) using 90°peel test. For that purpose both substrates were covered byapproximately 60 nm layers of gold and 25 mm wide tape with 20 Nadhesion to gold was applied to peel a stripe of gold from thesubstrates.

As a result the adhesion of gold to the Melinex ST506® substrate as usedin Comparison Example 2 is less or equal to 0.5N, whereas the adhesionof gold to the same substrate coated with a layer ofpoly(DMMIBuNB/TESNB) as used in Example 2, is >20 N.

The results of Example 1, 2 and 3 demonstrate that a substrate coatedwith a polynorbornene planarization layer provides largely improvedstability of OFETs compared to a prior art substrate as used inComparison Example 2, which is considered as a benchmark. Low surfaceroughness and high surface energy of polynorbornene layers are alsobeneficial for simplification of the OFET manufacturing process.Additionally, specific substituents, on the polynorbornene backbone,like triethoxysilyl (TES) as in formula (53), provide large increase ofadhesion to metals like gold, which eliminate the need for additionaladhesion layers between the planarization materials and the electrodes.

All the references described above are incorporated by reference intothis application.

1. An organic electronic device comprising a substrate, and provided onsaid substrate a functional layer selected from semiconducting layers,dielectric layers and electrodes, wherein a planarization layer isprovided between the substrate and the functional layer, wherein saidplanarization layer comprises a polycycloolefinic polymer.
 2. Theorganic electronic device of claim 1, wherein the polycycloolefinicpolymer is a norbornene-type polymer.
 3. The organic electronic deviceof claim 1, wherein the polycycloolefinic polymer comprises two or moredistinct types of repeating units.
 4. The organic electronic device ofclaim 1, wherein the polycycloolefinic polymer comprises a first type ofrepeating unit having a pendant crosslinkable group.
 5. The organicelectronic device of claim 4, wherein the pendant crosslinkable group isa latent crosslinkable group.
 6. The organic electronic device of claim5, wherein the pendant crosslinkable group comprises a substituted orunsubstituted maleimide portion, an epoxide portion, a vinyl portion, anacetylene portion, an indenyl portion, a cinnamate portion or a coumarinportion.
 7. The organic electronic device of claim 6, wherein the firsttype of repeating unit having a pendant crosslinkable group is derivedduring polymerization from one of the following monomers:

where n is an integer from 1 to 8, Q¹ and Q² are each independentlyselected from —H or —CH₃, and R′ in P4 is —H or —OCH₃.
 8. The organicelectronic device of claim 4, wherein the polycycloolefinic polymercomprises a second type of repeating units having a pendant silyl group.9. The organic electronic device of claim 1, wherein thepolycycloolefinic polymer comprises one or more distinct types ofrepeating units represented by formula I

wherein Z is selected from —CH₂—, —CH₂—CH₂— or —O—, m is an integer from0 to 5, each of R¹, R², R³ and R⁴ are independently selected from H, aC₁ to C₂₅ hydrocarbyl, a C₁ to C₂₅ halohydrocarbyl or a C₁ to C₂₅perhalocarbyl group.
 10. The organic electronic device of claim 9,wherein the polycycloolefinic polymer comprises one or more distincttypes of repeating units formed from norbornene-type monomersindependently selected from the following formulae:

wherein b is an integer from 1 to
 6. 11. The organic electronic deviceof claim 9, wherein the polycycloolefinic polymer comprises one or moredistinct types of repeating units formed from norbornene-type monomersindependently selected from the following formulae:


12. The organic electronic device of claim 9, wherein thepolycycloolefinic polymer comprises one or more distinct types ofrepeating units formed from norbornene-type monomers independentlyselected from the following formulae:


13. The organic electronic device of claim 1, wherein the planarizationlayer comprises two or more polycycloolefinic polymers having one ormore distinct types of repeating units of formula I

wherein Z is selected from —CH₂—, —CH₂—CH₂— or —O—, m is an integer from0 to 5, each of R¹, R², R³ and R⁴ are independently selected from H, aC₁ to C₂₅ hydrocarbyl, a C₁ to C₂₅ halohydrocarbyl or a C₁ to C₂₅perhalocarbyl group.
 14. The organic electronic device of claim 1,wherein the planarization layer is derived from a polymer compositioncomprising one or more of a solvent, a crosslinking agent, an optionalreactive solvent, a stabilizer, a UV sensitizer, an adhesion promoter,and a thermal sensitizer.
 15. The organic electronic device of claim 14,wherein the polymer composition comprises a compound selected of formulaIII1 or III2P-A″-X′-A″-P  III1H_(4−c)C(A″-P)_(c)  III2 wherein X′ is O, S, NH or a single bond, A″ isa single bond or a connecting, spacer or bridging group selected from(CZ₂)_(n), (CH₂)_(n)—(CH═CH)_(p)—(CH₂)_(n), (CH₂)_(n)—O—(CH₂)_(n),(CH₂)_(n)—C₆Q₁₀-(CH₂)_(n), and C(O), where each n is independently aninteger from 0 to 12, p is an integer from 1-6, Z is independently H orF, C₆Q₁₀ is cyclohexyl that is substituted with Q, Q is independently H,F, CH₃, CF₃ or OCH₃, P is a latent crosslinkable group, and c is 2, 3 or4, and where in formula III1 at least one of X′ and the two groups A″ isnot a single bond.
 16. The organic electronic device of claim 15,wherein the compound of formula III1 is selected of formula C1:

wherein R¹⁰ and R¹¹ are independently of each other H or a C₁-C₆ alkylgroup and A″ is as defined in claim
 15. 17. The organic electronicdevice of claim 14, wherein the polymer composition comprises a compoundof formula IVG-A″-P  IV wherein G is a surface-active group of the formula—SiR¹²R¹³R¹⁴, or a group of the formula —NH—SiR¹²R¹³R¹⁴, wherein R¹²,R¹³ and R¹⁴ are each independently selected from halogen, silazane,C₁-C₁₂-alkoxy, C₁-C₁₂-alkylamino, optionally substituted C₅-C₂₀-aryloxyand optionally substituted C₂-C₂₀-heteroaryloxy, and wherein one or twoof R¹², R¹³ and R¹⁴ may also denote C₁-C₁₂-alkyl, optionally substitutedC₅-C₂₀-aryl or optionally substituted C₂-C₂₀-heteroaryl, P is acrosslinkable group selected from a maleimide, a 3-monoalkyl-maleimide,a 3,4-dialkylmaleimide, an epoxy, a vinyl, an acetylene, an indenyl, acinnamate or a coumarin group, or comprises a substituted orunsubstituted maleimide portion, an epoxide portion, a vinyl portion, anacetylene portion, an indenyl portion, a cinnamate portion or a coumarinportion, and A″ is a single bond or a connecting, spacer or bridginggroup selected from (CZ₂)_(n), (CH₂)_(n)—(CH═CH)_(p)—(CH₂)_(n),(CH₂)_(n)—O, (CH₂)_(n)—O—(CH₂)_(n), (CH₂)_(n)—C₆Q₄-(CH₂)_(n),(CH₂)_(n)—C₆Q₁₀-(CH₂)_(n) and C(O)—O, where each n is independently aninteger from 0 to 12, p is an integer from 1-6, Z is independently H orF, C₆Q₄ is phenyl that is substituted with Q, C₆Q₁₀ is cyclohexyl thatis substituted with Q, Q is independently H, F, CH₃, CF₃ or OCH₃. 18.The organic electronic device of claim 17, wherein the compound offormula IV is selected of formula A1:

where R¹², R¹³ R¹⁴, and A″ are as defined in claim 17, and R¹⁰ and R¹¹are each independently H or a C₁-C₆ alkyl group.
 19. The organicelectronic device of claim 1, wherein the substrate is a polyester film.20. The organic electronic device of claim 19, wherein the substrate isa polyethyleneterephthalate (PET) or polyethylenenaphthalate (PEN) film.21. The organic electronic device of claim 1, wherein an electrode isformed on the planarization layer.
 22. The organic electronic device ofclaim 1, wherein an organic semiconductor layer is formed on theplanarization layer.
 23. The organic electronic device of claim 1,wherein a dielectric layer is formed on the planarization layer.
 24. Theorganic electronic device of claim 1, which is an Organic Field EffectTransistor (OFET), Organic Photovoltaic (OPV) Device, or Organic Sensor.25. The organic electronic device of claim 24, which is a top gate OFETor a bottom gate OFET.
 26. A product or assembly comprising an organicelectronic device of claim 1, which is an Integrated Circuit (IC), aRadio Frequency Identification (RFID) tag, a security marking orsecurity device containing an RFID tag, a Flat Panel Display (FPD), abackplane of an FPD, or a sensor.
 27. A process for preparing the topgate OFET of claim 25, comprising: a) depositing a layer ofplanarization material, which comprises a polycycloolefinic polymer or apolymer composition on a substrate, b) forming source and drainelectrodes on at least a portion of planarization layer, c) depositing alayer of organic semiconductor material over said planarization layerand source and drain electrodes, d) depositing a layer of dielectricmaterial on organic semiconductor layer, e) forming gate electrode on atleast a portion of dielectric layer and f) optionally depositing layer,which is an insulating and/or protection and/or stabilizing and/oradhesive layer, on the gate electrode and portions of dielectric layer.28. A process for preparing the bottom gate OFET of claim 25,comprising: a) depositing a layer of planarization material, whichcomprises a polycycloolefinic polymer or a polymer composition on asubstrate, b) forming gate electrode on at least a portion ofplanarization layer as depicted, c) depositing a layer of dielectricmaterial over said planarization layer and gate electrode, d) depositinga layer of organic semiconductor material) on dielectric layer, e)forming source and drain electrodes on at least a portion of organicsemiconductor layer as depicted, and f) optionally depositing layer,which is an insulating and/or protection and/or stabilizing and/oradhesive layer, on the source and drain electrodes and portions oforganic semiconductor layer.